Method of preparing zein solutions directly from gluten



Patented Nov. 6,1945

assasss I METHOD OF PREPARING ZEIN SOLUTIOKS DIRECTLY FROM' GLUTEN Roy a. cam, Chicago, 111., assignor to Time,

Incorporated, a corporation of New York No Drawing. Original application November 30,

A I 1942, Serial No.

467,402, now Patent No.

2,352,604, dated July 4, 1944. Divided and this application October 25, 1943, Serial No. 507,595

12 Claims. (onus-15s) This invention relates to methods of preparing commercially usable solutions and coating compositions of prolamines or prolamine-containing proteins directly from glutens, either corn, wheat, barley, etc. It is particularly directed to such methods which will produce solutions and coating compositions of the alcohol-soluble portion of corn gluten, of controlled solution and gelling characteristics.

This application is a division of my copending application, Serial No. 467,402, flled November 30, 1942, now Patent No. 2,352,604, granted July Heretofore, in the preparation of zein solutions and coating compositions, including the substantially non-aqueous .zein solutions and coating compositions of controlled solution and gelling characteristics as described in my prior Patent No. 2,185,110, granted December 26, 1939, for example, the zein is initially isolated from corn gluten and then dissolved in suitable solvents to form the desired solutions. To isolate zein from corn gluten as a commercially usable powder is a,

laborious and expensive process, involving steps of precipitation, settling, filtering, washing and drying. The. solubility of the zein in zein solvents and the solution characteristics such as stability and gelling tendencies. are largely dependent upon the care exercised in carrying out the steps of the process.

' In accordance with the present invention I prepare solutions of 'zein or zeincontaining proteins directly from corn gluten under conditions that will readily produce a wide variety of zein products in so far as properties and solubility characteristics are concerned, and thereby avoid the expense and objections incident to the preliminary isolation of zein in powder form. In carrying out the present'invention, corn gluten, for example, in granular or powdered form, is treated with a suitable solvent mixture, without the establishment of special conditions of hydrogen ion concentration either in the solvent or in the gluten, to extract the zein from the gluten. The

solvent mixture comprises a base solvent having a boiling'point above about 125 0., preferably above about 150 C. and a diluent or extender having a boiling point-below about 125 C. and, preferably, of about 100 C. and below. The base solvent is itself a solvent for zein and the diluent .may be, and preferably is, also a solvent for zein.

The base solvents and diluents in accordance with a the present invention will be defined fully hereafter.

The extraction is carried out at elevated temperatures, say from about 120 to about 170 F., preferably between about 140 to, about 150 F., for a short period of time generally not exceeding about three hours. It is preferred that the ex traction time be not longer than about one-half to about one hour since within this time and at the temperatures stated, the zein in the gluten is extracted and is not deleteriously afiect'ed.

The extract solution obtained as above described is now separated from the residual gluten by filtration, pressing, centrifugal separation or in any other desirable manner and is distilled or otherwise treated to remove all or some of the diluent, as desired. It may be filtered preliminarily to the step of removing the diluent, if necessary. The resulting residue is a solution of zein or zein-containing protein in the base solvent alone with all of the diluent from the extract solution removed, or in-the base solvent and that portion of the diluent which has not been removed. The residual gluten, which still contains some protein, may be freed from retained solvent bywashing and recovered for further use as a cattle food or for other purposes.

The resulting zein or zein-containing solutions in accordance with the present invention,

over a wide range of concentrations, are stable on standing at temperatures of 80 F. and below and do not separate even when cooled to temperatures of 50 to 70 F. and somewhat below. When cooled even to temperatures as low as 10 above zero or to zero, solutions prepared in accordance with the present invention may separate and become solid;'however, on heating again to temperature of from about 45 to 70 F., a resolution is efiected, either without stirring or with slight stirring, and the solutions return to their normal form at the re-heating temperatures. In general, these solutions are substantially non-gelling and have but a slight tendency to increase in viscosity; that is, to thicken or become heavier in body. In many instances they exhibit practically no tendency to thicken or to gel over practical period of time in the order of about 3 to 6 months and even up to one year and longer. These solutions remain stable and hydrocarbon radicals.

' quired balance of tween solvent and gluten for eflective extraction results. If large amounts of the relatively high boiling point base solvents are used, sumcient aseaasa to give the proper relation between solvent and gluten, the extraction results are not sufliciently eifective and, moreover, the cost of treating the extracts to obtain the desired solids concentration is so prohibitive as to make this procedure commercially unfeasibie.

The desired solvent to gluten ratio in accordance with the present invention is secured by adding to the desired amount of relatively high boiling point base solvent or mixture of base solvents one or more of the so-called relatively low boiling point diluent solvents. To obtain eflective extraction results, the solventto gluten ratio should be in the order of about 2% to parts by weight of the former to about 1 part-by weight of the latter. Due to the presence of a diluent or extender in the extracting solvent, the solvent to gluten ratio may be less than that which would be required with a base solvent alone and, notwithstanding the lower solvent to gluten ratio,

' the extraction results are generally more effective. The diluent solvent or extender must have a lower boiling point and distillation range than the base solvent. It is preferred that these diluent solvents or extenders be of substantially lower boiling point and distillation range than the base solvent. as pointed out above.

Bose solvents The'base solventsare relatively high boiling compounds or mixtures of compounds as pointed out above and have a suitable balance between the hydrocarbon constituents or radicals present in the solvent or solvent mixtures and the polar constituents or radicals present therein. A certain proportion of hydroxyl radicals in the base solvents is required to secure solvent action. Oth- 4 er polar radicals such as --O-(ether oxygen),

Cl, NH:| and COOH appear to aid or coop-- erate with the -OH in securing the necessary conditions of polarity in the base solvents (in which term I include mixtures of base solvents), for solventaction.

The proportion of polar radicals to hydrocarbon or non-polar-radicals which I have found to be desirable lies within a range which extends between the'limlts of absolute methanol on the one hand, having 53% hydroxyl and 47% hydrocarbon radicals, and absolute ethanol on the other hand having 37% hydroxyl and 63% as if it were intermediate the methyl and ethyl radicals. This range is approximate and may vary somewhat depending'on the solvent or solvent mixture used. The limits of this range are has the required balance of polar and non-polar 'radicals, and a boiling point above about 125 6., preferably, above about'150 C. as pointed out above. For a more complete description of the kinds of solvents which may be used as base solvents in accordance with the present invention than is disclosed herein, reference is made to the description of these. solvents in my prior Patent No. 2,185,110.

Examples of base solvents in accordance with the present invention are the glycols such as diethylene glycol, propylene glycol, triethylene glycol and mixtures thereof, including mixtures which contain ethylene glycol; diacetone alcohol; closed chain cyclic alcohols such as benzyl alcohol, cyclohexanol, iuriuryl alcohol, tetrahydroturiuryl alcohol and mixtures of closed chain alcohols; glycol ethers such as ethylene glycol mono-methyl ether, diethylene glycol mono methyl ether, ethylene glycol mono-ethyl ether, diethylene glycol monoethyl and mixtures of glycol ether-s; mixturesoi two or more oi the toregoi'ng enumerated base solvents; mixtures of one or more or the foregoing base solvents with glycerine, or other-solvents or mixtures of solvents,

providing the mixture has the required polar to non-polar radical balance and the required relatively high boiling point. It is tobe understood as desired. It is preferred, however, that the diluent or extender be asolvent for zein. Thus, the extending solvent may he one or more 01' the well-known alcoholic zein solvents such as sub!- The benzyl radical acts areas methanol. or constant boiling point mixtures (azeotropes) of aliphatic alcohols such as 5 95% ethyl alcohol and 91% isopropyl alcohol. rm-

convenience herein I term these alcoholic solvents "concentrated alcohol solvents. The diluent solvents may also be one or more 01' the concentrated alcohol solvents containing additional amounts of water, say from 40% to 50% in anhydrous methanol, or in excess oi that present inthe azeotropes 95% alcohol and 91% isopropyl alcohol. Greater or lesser amounts or water than as be used; however, best results are stated ma obtained with the use of added amounts of water within the percentage range stated. For convenience herein I term t'hese alcoholic solvents "aqueous alcohol mixtures.

Another class oi .dlluent solvents in accordance with the present invention comprises mixtures of an azeotropic. concentrated alcohol solvent with a non-solvent and water. Examples of such diluents are mixtures 01' 95% ethyl alcohol or 91% isoprepyl alcohol with. dichlorethylene, trichlorethylene, ethyl acetate, benzene, cyclohexane, etc., and water. In this class of diluent solvents I also include non-aqueous azeotropic mixtures of anhydrous methyl alcohol with hexane, cyclohexane, benzene, carbon tetrachloride, dichlorethylene, trichlorethylene, acetone, methyl acetate, ethylacetate, methyl ethyl ketone, etc. because one constituent of the mixture, methyl alcohol, is a zein solvent.

In addition to the foregoing, wherein at least one constituent of a diluent solvent mixture is a,

for illustrative pur- 2,ssa,sas

at 86.9 0.; and butyl alcohol forms with water a constant boiling point mixture containing 63% butyl alcohol boiling at 92 C. They .may also be suitable aqueous azeotroplc mixtures which are non-solvents for zein proteins such as ethyl methyl ketone and water. And they may also be non-aqueous azeotropic mixtures of anhydrous ethyl alcohol or anhydrous isopropyl alcohol with hexane, cyclohexane, benzene, carbon tetrachloride, dichlorethylene, trichlorethylene, acetone, methyl acetate, ethyl acetate, methyl ethyl ketone, etc.

The diluents may also be suitable non-solvents of low polarity characterized by the presence of -Cl, --NH:, -COOH groups, etc. Examples of such diluents are dioxan, dichlorpentane, ethylene dichloride, dichlorethyl ether, etc. They may also be miscible hydrocarbons such as benzene, hydrogenated naphtha, etc. Orv they may be centrated alcohol solvent alone or an aqueous alcohol mixture alone, approximately 2% parts by weight of solvent to l oi gluten may be used. At this concentration, with gluten containing approximately 60% total protein, the extract solutions of the concentrated alcohol solvent contain a maximum zein protein content of approximately whereas the extract solutions of the aqueous alcohol mixture solvents contain a maximum zein protein content of from about 12% to about 15% and even up to In addition, the aqueous alcohol mixture solvents are capable of extracting a substantially larger proportion of a desirable type 01' zein present in the protein of the gluten than are the concentrated alcohol solvents.

zein solutions of a desired concentration and o! a wide applicability can be obtained directly from gluten by having in the final solution as the only solvent or as the main solvent for zein, a relatively high boiling point solvent having the required balance of polar and non-polar radicals as described herein. It is now well established that the viscosi y, gelling tendencies, and practical usability of zein solutions are in no small part dependent upon the character ofthe solvent in which the zein is dissolved.

Zein or zein-containing extract solutions containing any one or more 01' the foregoing base solvents in accordance with'the present invention, may be boiled, distilled or otherwise treated to remove part or all of the diluent. It is evident that practically all of the diluent, including any water carried from the gluten to the extract solution, may be removed, thereby obtaining solutions 0! zein or zein-containing proteins, in the base solvent which, for all practical purposes, are substantially anhydrous. Such solutions vary widely in character, depending upon the choice of solvents or solventmixtures used. as is to be expected, and some oi them may undergo changes (apparent insolubility, for example), during the diluent and water removal which ailect the solvent characteristics of the zein and zein-containing proteins in the base solvent utilized. These changes, where they take place, are not oi a permanent character and it is possible to eflect a re-solution of the zein or zein-containing proteins in the base solvents bythe addition 01' a small a amount 01' water, say in the order of from about.

1 to 3% by weight, or an equivalent amount of other highly hydroxylated compound, such as methyl or ethyl. alcohol or a mixture of such compounds. 7

In the preparation of usable solutions having a wide field of applicability, I prefer that the removal of diluent and water be controlled so as to leave in the final solutions at least about 1 to 3% by weight of water or anequivalent amount of other highly hydroxylated compound, preferably water. Where this is not possible, water may be added to the final solution, in the amounts stated. While water is, in general, not an essential constituent of some of the solutions formed in accordance with the present invention, the solutions are generally of an improved character when they contain small amounts of water.

The solutions may contain larger amounts of water, say between 5 to 10%, or even more.

As already pointed out, the type or character of the zein-containing. protein produced by the extraction is in no small part dependent on the character of the extraction solvents used. This condition is particularly pronounced when the highly aqueous alcohols or the high water azeotropes such as dioxan-water or n-butyl alcoholwater mixtures are used as diluents. Not only do these diluents effect the extraction of a larger amount of the zein-containing protein than do the more concentrated alcohols, but they also produce by their extraction a type of zein protein which generally produces solutions having a high viscosity and pronounced colloidal consistency. On the other hand the zein protein produced with the concentrated alcohols and less aqueous diluents tends to produce solutions having a lower viscosity and a lesser colloidal consistency. It is thus evident that various types of zein protein having substantially diflerent properties can be produced by proper selection and composition of the diluents. From the foregoing it is manifest that the nature and properties 0! the finished solution will be determined by the nature of the base solvent, the amount of zein protein present in the solution and the type or character or the zein protein extracted by the particular diluent used. It is apparent that with the solvent and diluent combinations possible, a wide variety of solutions for many uses can be produced by the methods of the present invention.

Within the range of the many possible combinations and the methods in accordance with the present invention, solutions may be produced which require further adjustment or modification in order to secure improved solution or desired stability and controlled gelling properties. Such adjustments or modifications can be readily eftected by the use of rosin, fatty acids, compatible amines such. as monoethanolamine, triethanolamine, etc., amine soaps of rosin or fatty acids,

or by the various methods and materials for pro- 2,246,779 and 2.298.548. The addition or suitable materials for eilecting desired modification or adiustment may be made-to the extract solution 'beioredistillingolithediluentortotheflnalw lution. The preferable procedure and materials with particular solutions may be easily determined by experimentation.

In the following examples I disclose illustra tive methods for producing zein or aein-containing solutions directly from gluten in accordancewith the present invention. In the examples and elsewhere throughout the specification, the term in a vessel. The mixture wasflheated to about I 160 F. and held at about that temperature for about ti hour with stirring to extract the zeincontaining proteins from the gluten. The mixture was then forced through a filter to separate the rein-containing extract and the extract was then slowly heated to about 250 F. and held at about that temperature with stirring until cessation of visible boiling. The residue was a solution of zein-containing proteins principally in the mixture of glycols.

aaaasas trample 5.-,A solvent mixture containing 60 parts or a mixtureconsistingof 88.4% of ethyl methyl ketone and 11.6% of water, and 40 parts ofdietbylene glycol was added to 30 parts oi powdered gluten. The procedure was as in Example 1 except that the extraction temperature was 140' l". The resulting residue was a solution of seinqcontaining proteins principally in diethylene glycol Example 6.A solvent mixture containing 60 parts of a mixture consisting of 80% of denatured 95% ethyl alcohol (Paco") and of water, and 40 parts of a mixtureconsisting of 75% of diethylene glycol and %rethylene glycol monoethyl ether was added to parts of. powdered gluten. The procedure was as in Example 1 except that the extraction temperature was 140 F. The resulting residue was a solution of rein-containing proteins principally in the glycol and glycol ether mixture.

Emmple 7.-A solvent mixture containing 60 parts of a mixture consisting of 90% of 91% isopropanol and 10% of water, and parts or a mixture consisting of 75% of diethylene l col and 25% of ethylene glycol monomethyl ether was added to 30 parts of powdered gluten. The procedure was asin Example 1 except that the extraction temperature was 140 F. The resulting Example 2.--A solvent mixture containing 60 parts of a mixture consisting of 90% of denatured 95% alcohol (sold under the trade-mark .Paco) and 10% of water. and 40 parts of diacetone alcohol (acetone free) was added to 30 parts of powdered gluten in a vessel. The mixture was'heated to about 140 F. and held at about that temperature for about /2 hour with stirring to extract the zeta-containing proteins from the gluten. The mixture was then forced through a filter to separate the zein-containing extract and the extract was then slowly heated to about 220 F. and held at about that temperature until visible bubbling cased. At the end point the residue separated out into a heavy paste and clear supernatant solvent. Upon the addition of about 1 part of water to the residue, the separated residue came together into solution. This solution was a solution of rein-containing proteins. principally in the diacetone alcohol. v

In an additional e riment with the same ingredients and with the same procedure as outlined in Example 2 except that heating of the extract was discontinued while the extract was still bubbling, a solution .of the zein-containing proteins was obtained without the separation hereinabove pointed out. I

Inthe following examples the manipulative procedures were the same asthose set forth in Example 1, with the exceptions hereinafter noted, and in each instance the extracts were heated until cessation of visible boiling. 4

Elcample 3.-A solvent mixture containing 72 parts of a mixture consisting of 80% of dioxan and'20% of water, and 48 parts of diethylene 8'1!- residue was a solution or thezein-containing proteins principally in the .diethylene glycol and glycol ether mixture. I

Example 8.*A solvent mixture containing 60 parts of a mixture consisting of 80% of denatured 95% ethyl alcohol ("Paco") and 20% of water, and 40 parts of a mixture consisting of 75% of diethylene glycol and 25% of benzyl alcohol was added to 30 parts of powdered gluten. The procedure was as in Example 1 exceptthat the extraction temperature; was 140 F. The resulting residue was a solution of the zein-containing proteins principally in the diethylene glycol and benxyl alcohol mixture.

Example 9.-A solvent mixture containing parts of a mixture consisting of 90% of 95% ethyl alcohol and 10% of water, and 35 parts of benzyl alcohol was added to 30 parts of powdered gluten.

col was added to 30 parts of powdered gluten."

The procedure-was as in Example land the resulting residue was a solution of rein-containing proteins principally in diethylene glycol.

Example 4.-A solvent mixture containing parts of a mixture consisting of 63% of n-butanol and 37% of water, and 40 parts of diethylene glycol was added to 30 parts of powdered gluten. The-procedure was as in Example 1 except that the extraction temperature was 140 F. The resulting residue was a solution of rein-containing proteins princip ly in diethvlene'glycol.

The procedure was as in Example 2 except that the extraction temperature was F. The resulting residue was a solution of the rein-contain ingproteins principally in benzyl alcohol.

At the cessation of boiling asreferred tointhe examples some proportion of the lower boiling constituents of the diluent originally used remains' in the flnal solution. The proportion thereof so remaining depends upon the final temperature and the boiling point curve of the mixture. Considerable proportions of the diluent or of its constituents, including water, may remain without causing gelling o! the ilnal solution in reasonable periods of time. This is particularly truewheretheglycolsareused. Inthisrespect the final solutions show differences from solutions of commercial aein containing large amounts of water as in the prior art, apparentlyby reason of some changes in the character or structure of 'the min-containing proteins or the corn gluten taking place in the process of the present invention, the nature of which changes'is not as yet understood.

Ingeneraland influencedbythetype and amoimt of rein-protein present. the solutions prepared as described above and the coating compositions prepared therefrom have the prop. erties, particularly when heated, ofheing able to give up their-solvent. solvents readily. and

when applied to a surface they quickly and readily form tough, flexible, non-tacky, hard and generally transparent coatings even when retaining some solvent. The coatings formed by these zein containing solutions and coating compositions are very strong and have adherent properties. In these solutions and coating compositions the film forming properties thereof can be built up to produce films of great toughness, flexibility, hardness and gloss. Under normal temperature conditions, many of the zein-containing solutions or coating compositions will produce non-blushing coatings on drying, without the aid of supplementary antiblushing agents as in the prior art.

The coating compositions prepared from the above solutions may be modified and used as fully described in the aforementioned application Serial No. 467,402.

While my invention has been described in connection with certain specific examples, it is, of course, obvious it is not to be construed as limited to these examples or to the details of the methods set forth therein, since obvious changes in materials, proportions and method details will be ap-' parent from the foregoing. I v

In the claims, the expression an elevated tem-. perature in the order of about 120 F. to about 170 F. is not to be construed as a precise critical range, but, rather, as a range of temperaturesindicative of the elevated temperature at which the extractions may be carried out.

Iclaim: 1. The method of preparing directly from gluten a solution of zein-containins proteins in a solvent or mixture of solvents comprising as an essential solvent constituent for the zein-containing proteins, a solvent having a. boiling point above about 125 C. and having a proportion of polar to non-polar radicals which lies within a range extending between the limits of the proportion of polar to non-polar radicals of methanol and the proportion of polar to non-polar radicals of ethanol, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about 120 F. to about 170 F. to extract zein-containing proteins 'frorn the gluten, said solvent mixture comprising the aforesaid zein-containing Protein solvent having a boiling point above about 125 C. and an aqueous miscible diluent therefor having a boiling point below about 125 C., separating the extract from the residual gluten and removing at least part of the diluent from the extract to form the aforesaid solution.

; 2. The method of preparing directly from gluten a solution of zein-containing proteins in a solvent or mixture of solvents comprising as an taining proteins, a solvent having a boiling point above about 150 C. and having a proportion of polar to non-polar radicals which lies within a range extending between the limits of the proportion of polar to non-polar radicals of methanol and the proportion of polar to non-polar" radicals of ethanol, which comprises contacting all of the diluent from the extract to form above about 150 C. and having a proportion of essential solvent constituent for the zein-conpolar to non-polar radicals which lies within a range extending between the limit of the proportion of polar to non-polar radicals of methanol and the proportion of polar to non-polar radicals of ethanol, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about F. to about 170 F. to extract zein-containing proteins from the gluten, said solvent mixture comprising the aforesaid zein-containing protein solvent having a boiling point above about 150 C. and a miscible diluent therefor having a boiling point below about C., said diluent being an aqueous solvent for said zein-containing proteins, separating the extract from the residual gluten and removing at least part of the diluent from the extract to form the aforesaid solution.

4. The method of preparing directly from gluten-a solution of zein-containing proteins in a solvent or mixture of solvents comprising as an essential solvent constituent for the zein-containing proteins, a solvent having a boiling point' above about C. and having a proportion of polar to non-polar radicals which lies within a range extending between the limits of the proportion of polar to non-polar radicals of methanol and the proportion of polar to non-polar radicals of ethanol, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about 120 F. to about F. to extract zein-containing proteins from the gluten, said solvent mixture comprising the aforesaid zein-containing protein solvent having a boiling point above about 150 C. and a miscible diluent therefor having a, boiling point below about 125 C., said diluent comprising an azeotropic mixture of an alcohol and water which is a solvent for said zein-containing proteins and an additional amount of water in excess of that present in the azeotrope, separating the extract from the residual gluten and removing at least part of the diluent from the extract to form the aforesaid solution.

5. The method of preparing directly from gluten solution of zein-containing proteins in a solvent or mixture of solvents comprising as an essential solvent constituent for the zeimcontaining proteins, a solvent having a boiling point above about 150 C. and having a proportion of polar to non-polar radicals which lies within a range extending between the limits of the proportion of polar to non-polar radicals of methanol and the proportion of polar to non-polar radicals of ethanol, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about 120 F. to about 170 F. to extract zein-containing proteins from the gluten, said solvent mixture comprising the aforesaid zein-containing protein solvent having a boiling point above about 150 C. and a miscible diluent therefor having a boiling point below about 100 (3., said diluent comprising an azeotropic. mixtureof an aliphatic alcohol having from two to three carbon atoms in the molecule and water which is a solvent for said zein-containing proteins and an additional amount of Water in excess of that present in the azeotrope,

separating the extract from the residual gluten and removing at least part of the diluent from the extract to form the aforesaid solution.

6. The method of preparing directly from gluten a solution of min-containing proteins in a solvent or mixture of solvents comprising diacetone alcohol'as an essential solvent constituent for the roin-containing proteins, which comprises contacting gluten with asolvent mixture at an tone alcohol as an essential solvent constituent for the zeincontainlng proteins, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about 120 F. to about 170 F. to extract zein-containing proteins from the gluten, said solvent mixture comprising diacetone alcohol andan aqueous miscible diluent therefor having a boiling point below about 125 C., said diluent being a solvent for said zein-containing proteins, separating the-extract from the'residuai gluten and removing at least part of the diluent from the extract to form the aforesaid solution.

8. The method of preparing directly from gluten a solution of min-containing proteins in a solvent or mixture of solvents comprising benzyl alcohol as an essential solvent constituent for the zein-containing proteins, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about 120 F. to about 170 F. to extract. zein-containing proteins from the gluten, said solvent mixture comprising benzyl alcohol and an aqueous miscible diluent therefor having a boiling point below about 125 C., said diluent being a solvent for said min-containing proteins, separating the extract from the residual gluten and removing at least 's,sss,sss

gluten with a. solvent mixture at an elevated temperatureintheorderolaboutm lltoabout proteins, separating the extract from the residualgluten and removing at least part otthe diluent from the extract to form the aforesaid solution.

10. The method of preparing directly from .gluten a solution of stein-containing proteins in a solvent or mixture of solvents comprising discetone alcohol as an essential solvent constituent for the min-containing proteins, which comprises contacting gluten with a solvent mixture at an alcohol and water from the extract to form the elevated temperature in the order of about 120' I. to about 170 1''. to extract min-containing proteins from the gluten, said solvent mixture comprising diacetone alcohol, ethyl alcohol and water, separatingthe-extract from the residual gluten and removing-at least part of the ethyl aforesaid solution.

11. The method of preparing directly from gluten 9. solution of min-containing proteins in'a mixture of solvents comprising diethylene glycol and ethylene glycolmonomethyl ether as essential solvent constituents for the win-containing proteins, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about I". to about 1". to extract zein-containing proteins from the gluten, said solvent mixture comprising diethylene glycol, ethylene glycol monomethyl ether, 91% isopropyl alcohol and water, separating the extract from the residual gluten and removing at least part -of the lsopropyl alcohol and water from the extract to form the aforesaid solution. I

12. The method of preparing directly from gluten a solution of min-containing proteins in a part of the diluent from the extract to form the o containing proteins, which comprises contactingv solvent or mixture of solvents comprising benzyl alcohol as an essential solvent constituent for the rein-containing prdseins, which comprises contacting gluten with a solvent mixture at an elevated temperature in the order of about 120' 1". to about 170 1". to extract sein-containing' proteins from the gluten, said solvent mixture comprising benzyl alcohol, 95% ethyl alcohol and water, separating the extract from the residual gluten and removing at' least part of the 95% ethyl alcohol and water from the extract to form the aforesaid solution.

a ROY E. COL-KHAN. 

